US4222853A - Application of sulfosuccinic ester anti-fouling agents - Google Patents

Application of sulfosuccinic ester anti-fouling agents Download PDF

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Publication number
US4222853A
US4222853A US06/025,450 US2545079A US4222853A US 4222853 A US4222853 A US 4222853A US 2545079 A US2545079 A US 2545079A US 4222853 A US4222853 A US 4222853A
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United States
Prior art keywords
fouling
crude petroleum
metal
group
agents
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US06/025,450
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English (en)
Inventor
Claude Scherrer
Marc Durrieu
John R. Richmond
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universal Matthey Products SA
Compagnie Francaise de Raffinage SA
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Universal Matthey Products SA
Compagnie Francaise de Raffinage SA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/10—Inhibiting corrosion during distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/949—Miscellaneous considerations
    • Y10S585/95—Prevention or removal of corrosion or solid deposits

Definitions

  • the invention concerns new anti-fouling agents and the application of said agents to the treatment of crude petroleum.
  • a current problem in the petroleum refining industry is that posed by the fouling of equipment, such as for example, heat exchangers, into which charges from different units of a refinery pass.
  • equipment such as for example, heat exchangers
  • deposits attributed to the presence of organic or inorganic materials in the charges form on the interior at these heat exchangers.
  • this fouling is complex and varied; this fouling can be provoked by accumulations of oxidation products, asphaltene deposits, salts or by scaling phenomena.
  • the deposits are constituted by 50 to 70% by weight of mineral compounds, notably compounds of iron (oxides, sulfides) and by 50 to 30% of organic compounds (asphaltenes, carbenes). It may also be due to organic compounds which polymerize under the action of heat, oxides or oxygen dissolved in the crude petroleum.
  • the fouling of these exchangers involves, besides very frequent cleaning operations, an increase in the consumption of energy necessary to heat the charge, due to the loss in efficiency of the exchangers.
  • the use of anti-fouling agents is an economic means to combat this fouling.
  • the anti-fouling agent is a chemical product which is added to the charge in very low concentrations, in the order of several parts per million by volume. Numerous types of anti-fouling agents have already been employed, such as, for example, agents based on phosphoric esters.
  • the aim of the present invention is therefore to provide novel anti-fouling agents.
  • the present invention has, as its primary object, novel anti-fouling agents capable of at least diminishing the fouling of equipment in contact with a charge of crude petroleum, said agents being characterized in that they are constituted, in part or in whole, by at least one compound selected from the group consisting of those having the formula: ##STR2## where R and R' are linear or branched alkyl radicals having between 4 and 12 carbon atoms and where M is an atom of a metal of Groups IA and IIA of the Periodic Table, with:
  • n 1 when the metal M is a metal of Group IA, and
  • n 2, when the metal M is a metal of Group IIA.
  • a second object of the invention is the application of the anti-fouling agents represented by the above formula to the treatment of crude petroleum.
  • the inventors have thus used with success sodium di-2-ethylhexylsulfosuccinate as an anti-fouling agent for crude petroleum.
  • the anti-fouling agents according to the invention can be particularly used for the treatment of crude petroleum subject to distillation under atmospheric pressure.
  • the crude petroleum, preheated in a first series of exchangers Prior to distillation under atmospheric pressure, the crude petroleum, preheated in a first series of exchangers is submitted to a desalting operation in a desalting unit, then preheated in a second series of exchangers, before introduction into the oven preceding the distillation tower.
  • the anti-fouling agent can, for example, be introduced into the crude petroleum after it leaves the desalting unit and before it enters the second series of preheating exchangers.
  • the anti-fouling agent can also be introduced into the crude petroleum directly in the desalting unit, as the de-emulsifying agent capable of breaking the stable emulsions which can form therein, as described in the French patent application No. 77 11 906 previously cited.
  • the agent has therefore, in this case, both a de-emulsifying action on the stable emulsion and an anti-fouling action.
  • the agent is injected into the desalting unit, at the level where the stable emulsion is apt to form, by using a suitable introducing system.
  • This injection can be made in a discontinuous manner, when the stable emulsion is detected, and/or in a continuous manner in order to avoid the formation of a stable emulsion and/or to avoid the deposit of the stable emulsion on the introducing system.
  • the anti-fouling and de-emulsifying agent thus introduced into the crude phase contained in the desalted material, is entrained thereby in the second series of exchangers and by its presence contributes to avoiding the fouling of said exchangers.
  • the anti-fouling agents can be introduced into the crude petroleum in solution in hydrocarbons.
  • the anti-fouling agents are used in an amount such that the crude petroleum passing through the exchangers contains preferably a maximum of 100 ppm by volume of the anti-fouling agent with respect to the volume of the crude petroleum. This higher limit of 100 ppm is only justified by the cost of the anti-fouling agent.
  • FIG. 1 is a schematic section of a pilot exchanger in which the Examples were carried out:
  • FIGS. 2 and 3 illustrate the variation in the resistance of the deposits as a function of time calculated from the results of these tests.
  • This example is intended to illustrate the lowering of the fouling of an exchanger for a crude petroleum when there is introduced into this crude petroleum at the exit of the desalting unit, an anti-fouling agent according to the invention.
  • Control test TA1 is a comparative test carried out with a desalted crude Iraqi petroleum KIRKOUK not containing any anti-fouling agent,
  • TA2 is a comparative test carried out with the same crude petroleum containing 80 ppm by volume of a commercial anti-fouling agent bases on a phosphoric ester, containing 50% of active material,
  • Test A is a test carried out with the same crude petroleum containing an anti-fouling agent according to the invention, in the amount of 80 ppm by volume, comprising a solution of 50% of sodium di-2-ethylhexyl-sulfosuccinate in a heavy aromatic solvent.
  • Tests TA2 and A were thus carried out with the addition to the crude petroleum of the same quantity of active material of the anti-fouling agent.
  • Tests TA1, TA2 and A were carried out in a pilot exchanger such as represented in FIG. 1.
  • This exchanger consists of a tube 1, placed coaxially in a tube 2.
  • Tube 1 is a tube having an exterior diameter of 1.372 cm and an interior diameter of 0.925 cm ("schedule" No. 40: see WUITHIER Raffinage et Genie Chimique, Vol. II, page 1051).
  • Tube 2 is a tube having an exterior diameter of 2.667 cm and an interior diameter of 2.093 cm ("schedule" No. 40).
  • the length of tubes 1 and 2 is 2 meters.
  • the crude petroleum circulates in tube 1, in the direction indicated by arrow A.
  • a heat transfer fluid circulates in tube 2 in the direction indicated by arrow B. Therefore a simple counter-current exchange is involved.
  • the flow rates of the crude petroleum and of the heat transfer fluid were kept constant at a value of 5 1/hr.
  • the inlet temperature of the crude petroleum in tube 1 was maintained constant at 140° C.
  • the inlet temperature of the heat transfer fluid in tube 2 was maintained constant at 310° C.
  • the exit temperatures of the crude petroleum in tube 1 and of the heat-transfer fluid in tube 2 vary as a function of the degree of fouling and, from these temperatures, the transfer coefficient of the exchanger can be calculated (see for example WUITHIER, Raffinage et Genie Chimique, Vol. II--page 1059 ff)
  • FIG. 2 there are shown the straight lines obtained with the results of Tests TA1, TA2 and A.
  • the slopes of these straight lines show the speed of fouling.
  • the velocity of fouling is thus reduced by 58%, if there is added to the crude petroleum an anti-fouling agent according to the invention whereas it is only reduced by 24% by adding a conventional anti-fouling agent.
  • the use of an anti-fouling agent according to the invention permits practically doubling the interval between two cleanings of the exchanger.
  • This example is intended to illustrate the lowering of the fouling of an exchanger for crude petroleum when there is introduced into the desalting unit, to eliminate the stable emulsion which forms therein, an anti-fouling agent according to the invention.
  • Control test TB was carried out with a crude desalted petroleum from a field in Saudi Arabia (light Arabian). This petroleum contains 6% by weight of a stable emulsion, this emulsion containing itself:
  • Test B was carried out with the same desalted crude petroleum but not containing a stable emulsion, this having been destroyed in the desalting unit by continuous injection at the water-crude interface of 20 ppm by volume with respect to the crude petroleum of an anti-fouling agent according to the invention, consisting of a solution of 50% sodium di-2-ethylhexylsulfosuccinate in a heavy aromatic solvent.
  • FIG. 3 are shown the straight lines obtained with the results of tests TB and B.
  • the speed of fouling is thus reduced by 73% if there is added to the crude petroleum in the desalting unit in order to destroy the stable emulsion, an anti-fouling agent according to the invention.
  • Examples 1 and 2 thus show the efficacy of an anti-fouling agent according to the invention to combat the fouling of exchangers when this agent is injected into the desalting unit or after the desalting unit.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US06/025,450 1978-04-04 1979-03-28 Application of sulfosuccinic ester anti-fouling agents Expired - Lifetime US4222853A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7809855A FR2421958A1 (fr) 1978-04-04 1978-04-04 Nouveaux agents anti-salissures et application desdits agents
FR7809855 1978-04-04

Publications (1)

Publication Number Publication Date
US4222853A true US4222853A (en) 1980-09-16

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Country Status (10)

Country Link
US (1) US4222853A (fr)
JP (1) JPS5558290A (fr)
BE (1) BE875293A (fr)
CA (1) CA1122136A (fr)
DE (1) DE2910499A1 (fr)
FR (1) FR2421958A1 (fr)
GB (1) GB2017747B (fr)
IT (1) IT1112991B (fr)
NL (1) NL187586C (fr)
SE (1) SE445118B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670163A (en) * 1985-05-29 1987-06-02 Phillips Petroleum Company Inhibiting corrosion
FR2609648A1 (fr) * 1987-01-16 1988-07-22 Total France Agent desemulsifiant et antisalissure apte a separer des melanges eau-hydrocarbures, eventuellement mis en emulsion, et applications de cet agent
US4889614A (en) * 1989-05-09 1989-12-26 Betz Laboratories, Inc. Methods for retarding coke formation during pyrolytic hydrocarbon processing
WO2019008329A1 (fr) 2017-07-06 2019-01-10 Innospec Oil Field Chemicals Llc Compositions et procédés et utilisations associées

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4775459A (en) * 1986-11-14 1988-10-04 Betz Laboratories, Inc. Method for controlling fouling deposit formation in petroleum hydrocarbons or petrochemicals
GB8925535D0 (en) * 1989-11-11 1990-01-04 Rechem Ag Gasoline composition
AT400149B (de) * 1993-08-17 1995-10-25 Oemv Ag Additiv für unverbleite ottokraftstoffe sowie dieses enthaltender kraftstoff
US10242737B1 (en) * 2018-02-13 2019-03-26 Macronix International Co., Ltd. Device structure for neuromorphic computing system

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2548630A (en) * 1947-08-21 1951-04-10 Standard Oil Co Method of preventing corrosion in pipe-line transportation of refined petroleum oils
US2579890A (en) * 1948-07-03 1951-12-25 Shell Dev Nonclogging distillate fuel oil
US2948596A (en) * 1955-12-20 1960-08-09 Gulf Research Development Co Non-stalling gasoline fuel compositions
US3105810A (en) * 1959-01-19 1963-10-01 Nalco Chemical Co Preventing fouling of metal conductors in a refinery process
US3116128A (en) * 1959-12-28 1963-12-31 Gulf Research Development Co Fuel oil composition and composite improvement agent therefor
FR1488184A (fr) * 1965-08-04 1967-07-07 Shell Int Research Perfectionnement des combustibles pour moteurs et du fonctionnement des moteurs
US3776835A (en) * 1972-02-23 1973-12-04 Union Oil Co Fouling rate reduction in hydrocarbon streams
US3920572A (en) * 1973-04-18 1975-11-18 Chevron Res Heat transfer fluids
US4107030A (en) * 1976-06-03 1978-08-15 Nalco Chemical Company Antifoulants for crude oil

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2548630A (en) * 1947-08-21 1951-04-10 Standard Oil Co Method of preventing corrosion in pipe-line transportation of refined petroleum oils
US2579890A (en) * 1948-07-03 1951-12-25 Shell Dev Nonclogging distillate fuel oil
US2948596A (en) * 1955-12-20 1960-08-09 Gulf Research Development Co Non-stalling gasoline fuel compositions
US3105810A (en) * 1959-01-19 1963-10-01 Nalco Chemical Co Preventing fouling of metal conductors in a refinery process
US3116128A (en) * 1959-12-28 1963-12-31 Gulf Research Development Co Fuel oil composition and composite improvement agent therefor
FR1488184A (fr) * 1965-08-04 1967-07-07 Shell Int Research Perfectionnement des combustibles pour moteurs et du fonctionnement des moteurs
US3776835A (en) * 1972-02-23 1973-12-04 Union Oil Co Fouling rate reduction in hydrocarbon streams
US3920572A (en) * 1973-04-18 1975-11-18 Chevron Res Heat transfer fluids
US4107030A (en) * 1976-06-03 1978-08-15 Nalco Chemical Company Antifoulants for crude oil

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670163A (en) * 1985-05-29 1987-06-02 Phillips Petroleum Company Inhibiting corrosion
FR2609648A1 (fr) * 1987-01-16 1988-07-22 Total France Agent desemulsifiant et antisalissure apte a separer des melanges eau-hydrocarbures, eventuellement mis en emulsion, et applications de cet agent
EP0277060A1 (fr) * 1987-01-16 1988-08-03 Compagnie De Raffinage Et De Distribution Total France Agent désémulsifiant et antisalissure apte à séparer des mélanges eau-hydrocarbures, éventuellement mis en émulsion, et applications de cet agent
US5154857A (en) * 1987-01-16 1992-10-13 Compagnie De Raffinage Et De Distribution Total France Demulsifying and antifouling agent suitable for separating possibly emulsified water/hydrocarbon mixtures
US4889614A (en) * 1989-05-09 1989-12-26 Betz Laboratories, Inc. Methods for retarding coke formation during pyrolytic hydrocarbon processing
WO2019008329A1 (fr) 2017-07-06 2019-01-10 Innospec Oil Field Chemicals Llc Compositions et procédés et utilisations associées
CN111164180A (zh) * 2017-07-06 2020-05-15 英诺斯帕油田化工有限责任公司 组合物及其相关方法和用途
US11566164B2 (en) 2017-07-06 2023-01-31 Innospec Oil Field Chemicals Llc Compositions and methods and uses relating thereto

Also Published As

Publication number Publication date
SE445118B (sv) 1986-06-02
FR2421958B1 (fr) 1980-10-31
SE7902906L (sv) 1979-10-05
GB2017747B (en) 1982-09-02
JPS6160880B2 (fr) 1986-12-23
NL7902660A (nl) 1979-10-08
GB2017747A (en) 1979-10-10
DE2910499A1 (de) 1979-10-18
IT7921468A0 (it) 1979-03-30
FR2421958A1 (fr) 1979-11-02
BE875293A (fr) 1979-10-03
NL187586C (nl) 1991-11-18
CA1122136A (fr) 1982-04-20
DE2910499C2 (fr) 1989-07-06
JPS5558290A (en) 1980-04-30
IT1112991B (it) 1986-01-20

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